Preparation of Styrene Acrylic

PREPARATION OF STYRENE ACRYLIC

COPOLYMER TONER RESIN BY SOLUTION

POLYMERIZATION

NEO SU SIANG

DISERTATION SUBMITTED IN

FULFILMENT OF THE REQUIREMENTS

FOR THE DEGREE OF MASTER OF

SCIENCE

FACULTY OF SCIENCE

UNIVERSITY OF MALAYA

KUALA LUMPUR

APRIL 2010

ii

ACKNOWLEDGEMENT

I would like to extend my appreciation and gratitude to Prof Dr Gan Seng Neon

and Dr Mohd Tahir Abdul Rahman for their patience, help, encouragement and advices

throughout this work.

I would like to express my sincere gratitude to the staff members of the

Chemistry Department, Faculty of Science, University Malaya for their cooperation and

support, I take this opportunity to acknowledge the financial assistance of Jadi Imaging

Technologies Sdn Bhd.

Finally, I would like to thank my parents, Neo Sewi Yang and Ong Yew Choo,

for their genuine care, unfailing help and support.

iii

ABSTRACT

This project has investigated solution polymerization to produce toner resins.

There are three stages: (i) synthesis of low molecular weight styrene acrylic copolymer;

(ii) synthesis of high molecular weight styrene acrylic copolymer; (iii) mixing high and

low molecular weight copolymers. Gel Permeation Chromatography (GPC) was used

to study molecular weight distributions, Melt Flow Index (MFI) Instrument to study the

flowability of resin, Differential Scanning Calorimetry (DSC) to study the thermal

properties of resin, and acid number to quantitate the amount of acidic group in the resin.

A comparison of properties between the experimental samples, patents claims, and

commercial resins had been carried out. Preparation of low molecular weight resin has

carried out by using monomers, initiator and solvent. The effects of initiator

concentration on the resins properties of low molecular weight resin had been studied.

High molecular weight resin was produced by using monomers, initiator, solvent and

crosslinking agent in the system. The process started with bulk polymerization

followed by solution polymerization. The variation on amount of tetra(ethylene

glycol)diacrylate (TD) during solution polymerization was carried out to study the

effects on resins properties. Commercial toner resins contain a high molecular weight

portion and a low molecular weight portion. The commercial resins have glass

transition temperature in the range of 63~66C, Melt Flow Index in the range of 4~10

g/10 min, and acid number in the range of 8.5~10.2 mg KOH g-1. As for high molecular

weight portion, Mn is in the range of 1.93105~3.0210

5 gmol

-1, Mp in the range of

8.07105~1.710

6 gmol

-1, Mw in the range of 5.510

5~6.7710

5 gmol

-1, Mz in the range

of 1.2106~1.510

6 gmol

-1, polydispersity in the range of 2.24~3.92. While for low

molecular weight portion, Mn is roughly 4103 gmol

-1, Mp around 510

3 gmol

-1, Mw in

the range of 6103~710

3 gmol

-1, Mz in the range of 910

3~1.110

4 gmol

-1,

polydispersity in the range of 1.68~1.80. The ratio of low molecular weight portion to

iv

high molecular weight portion varies from 36:64 to 60:40. In this project, the low and

high molecular weight portions were synthesized separately and they were mixed at

various proportions to achieve the required properties as toner resins.

v

ABSTRAK

Tujuan utama projek ini adalah untuk menghasilkan resin toner yang melibatkan

tiga peringkat eksperimen. (i) sintesis kopolimer stirena akrilik berberat molekul rendah;

(ii) sintesis kopolimer stirena akrilik berberat molekul tinggi; (iii) percampuran kedua-

dua kopolimer berberat molekul rendah dan tinggi. Kromatograf Penelapan Gel (GPC)

telah diguna untuk mengkaji taburan berat molekul; Alat Indeks Aliran Leburan (MFI)

diguna untuk mengkaji keupayaan leburan resin beralir; Kalorimetri Pengimbasan

Pembezaan (DSC) untuk mengkaji sifat therma and nombor asid (AN) untuk mengkaji

kandungan asid yang terdapat dalam resin. Satu perbandingan di antara resin

perdagangan, paten US dan sampel eksperimen telah dianalisiskan. Resin berberat

molekul rendah adalah disintesis melalui proses pempolimeran larutan dengan

menggunakan hanya pelarut, monomer dan initiator. Manakala, resin berberat molekul

tinggi adalah disediakan melalui proses pempolimeran bulk diikuti dengan

pempolimeran larutan dengan menggunakan monomer, pelarut, initiator dan juga agen

crosslinking. Dengan merujuk kepada resin perdagangan, terdapat dua bahagian dalam

resin tersebut; bahagian berberat molekul rendah dan bahagian berberat molekul tinggi.

Merujuk kepada resin perdagangan, Tg adalah dalam linkungan 63~66C, MFI dalam

linkungan 4~10 g/10 min, dan AN dalam linkungan 8.5~10.2 mg KOH/g. Keputusan

GPC untuk bahagian berberat molekul tinggi, Mn dalam linkungan 1.93x105~3.02x10

5

gmol-1, Mp dalam linkungan 8.07x10

5~1.7x10

6 gmol

-1, Mw dalam linkungan

5.5x105~6.77x10

5 gmol

-1, Mz dalam linkungan 1.2x10

6~1.5x10

6 gmol

-1 dan Ip dalam

linkungan 2.24~3.92. Manakala untuk bahagian berberat molekul rendah, Mn adalah

dalam linkungan 3.5x103~3.8x10

3 gmol

-1, Mp dalam linkungan 4.7x10

3~4.9x10

3 gmol

-1,

Mw dalam linkungan 5.9x103~6.9x10

3 gmol

-1, Mz dalam linkungan 9x10

3~1.1x10

4

gmol-1 dan Ip dalam linkungan 1.68~1.80. Nisbah bahagian berberat molecul tinggi

kepada bahagian berberat molecul rendah berubah daripada 36:64 kepada 60:40. Dalam

vi

projek ini, bahagian resin berberat molekul tinggi dan rendah adalah disintesis

berasingan dan dicampurkan dalam pelbagai nisbah untuk mencapai sifat-sifat yang

diperlukan oleh toner resin.

CONTENT

ACKNOWLEDGEMENT ii

vii

ABSTRACT iii

ABSTRAK v

CONTENT vii

LIST OF FIGURES xi

LIST OF TABLES xiv

LIST OF ABBREVIATIONS xvi

CHAPTER ONE: INTRODUCTION

1.1 Laser Printer 1

1.2 Toner 3

1.3 Print Defects 7

1.4 Bulk and Solution Polymerization 8

1.5 Mechanism for Free Radical Addition Polymerization 12

1.6 Thermal Initiation in Absence of an Initiator 13

1.7 Radical Initiator 14

1.8 Transfer Constants in Free Radical Polymerization 15

1.9 Crosslinking Reaction in Free Radical Polymerization 16

1.10 Styrene acrylic Copolymerization 18

1.11 Selection of Monomer 22

1.12 Scope of Study 22

CHAPTER TWO: EXPERIMENTAL

2.1 Synthesis of Low Molecular Weight Styrene acrylic

Copolymer

23

2.1.1 Materials 23

2.1.2 Apparatus 23

2.1.3 Formulations 24

viii

2.1.4 Process 24

2.1.5 Sample Drying 25

2.2 Synthesis of High Molecular Weight Styrene acrylic

Copolymer

25

2.2.1 Materials 25

2.2.2 Apparatus 25


2.2.4 Process 27


2.3 Mixing of High and Low Molecular Weight Styrene acrylic

Copolymer

29

2.3.1 Materials 29

2.3.2 Apparatus 29


2.3.4 Processes 30


2.4 Characterization for Series of Styrene acrylic Copolymer 31

2.4.1 DSC 31

2.4.2 GPC 32

2.4.3 MFI 33

2.4.4 AN 34

2.4.5 TSC 35

2.5 Preparation of Finished Toner by using Pilot Plant 36

2.5.1 Materials 36


2.5.3 Pilot Line Processes 37

ix

2.6 Print Test 43

2.7 Toner Characterization 44

2.7.1 Apparent Density 44

2.7.2 Flowability 45

2.7.3 Tribocharge 46

2.7.4 Magnetic Content 47

2.7.5 Particle Size Distribution 48

CHAPTER THREE: RESULTS AND DISCUSSIONS

3.1 Characterization for Low Molecular Weight Styrene acrylic

Copolymer

49

3.1.1 DSC 49

3.1.2 GPC 49

3.1.3 MFI 52

3.1.4 AN 53

3.1.5 TSC 55

3.1.6 Summary for Low Molecular Weight Resin 56

3.2 Characterization for High Molecular Weight Styrene acrylic

Copolymer

60

3.2.1 Summary for High Molecular Weight Resin 60

3.3 Characterization for Mixture of High and Low Molecular

Weight Styrene acrylic Copolymer

67

3.3.1 Determination of GPC Peak Ratio 67

3.3.2 Calculation for Mixing Ratio 69

3.3.3 Summary for Mixed Resin 71

3.4 Characterization for Styrene acrylic Commercial Resin 74

x

3.4.1 Summary for Commercial Resins 74

3.5 Print Test 77

CHAPTER FOUR: CONCLUSION

4.1 Summary 80

4.2 Further Works as Extension to the Project 81

List of Figure

Figure 1.1 The basic components of a laser printer includes fuser, 2

xi

photoreceptor drum assembly, developer roller, laser

scanning unit, toner hopper, corona wire and discharge lamp

Figure 1.2 Comparison between manufacturing processes of

conventional toner with chemically prepared toner

5

Figure 1.3 Picture of conventional toner resin particles under 3 Mega

Pixel camera by magnification 10

6

Figure 1.4 Mechanism of thermal polymerization for styrene, which

involve initial formation of Diels-Alder dimmer (compound

A in figure 1.4), which transfers a hydrogen atom to

monomer to yield an initiator styryl radical (compound B in

figure 1.4) and a benzylic radical (compound C in figure 1.4).

14

Figure 1.5 Copolymer configurations can be either in random,

alternating, block or graft configuration depends on the

comonomer reactivity and concentration as well as the

polymerization condition and processes

21

Figure 2.1 Apparatus set up for preparation of low molecular weight

resin (A: mechanical stirrer, B: digital thermometer, C:

heater, D: reactor flask, E: oil bath)

23

Figure 2.2 Apparatus set up for preparation of high molecular weight

resin (A: mechanical stirrer, B: digital thermometer, C:

heater, D: reactor flask, E: oil bath)

25

Figure 2.3 Glass tray contained precipitated polymer (before dried in

oven)

28

Figure 2.4 Apparatus for mixing of high and low molecular weight

resins

29

Figure 2.5 DSC 31

xii

Figure 2.6 GPC 32

Figure 2.7 MFI 33

Figure 2.8 Aluminium cups contained dried polymer samples 36

Figure 2.9 Processes to produce finished toner 38

Figure 2.10 Mixer used to mix the resin, magnetite pigment, wax and

charge control agent.

39

Figure 2.11 Extruder was used to melt the mixture and extrude the

mixture of resin, magnetite pigment, wax and charge control

agent.

40

Figure 2.12 Crusher was used to crush down the extruded mixture into

rough powder

41

Figure 2.13 Miller was used to reduce the size of the rough powder,

wherein classifier was used to produce toner powder in more

even sizes.

42

Figure 2.14 Blender was used to blend the toner powder together with

magnetite pigment, silica and zinc stearate to produce a

finished toner.

43

Figure 2.15 Apparent density equipment (A: sample hopper, B: sample

container)

44

Figure 2.16 Flowability equipment (A: sample hopper, B: sample

container, C: disc with different pore size)

45

Figure 2.17 Keithley Instruments 610C solid state electrometer (A:

sample container)

46

Figure 2.18 Tectron Ag. 916 Fluxmeter 47

Figure 2.19 CILAS 1064 particle size analyzer 48

Figure 3.1 GPC curve for low molecular weight resin 51

xiii

Figure 3.2 GPC curve for high molecular weight sample 51

Figure 3.3 Phenolphthalein appear colourless in acidic system (pH 0 to

8.2) and appear in pink colour when the system change to

alkaline (pH 8.2 to 12)

53

Figure 3.4 Mechanism of MAA incorporated into the copolymer 63

Figure 3.5 Generation of radical for TD in the polymerization system 65

Figure 3.6 Network morphology in the crosslinking reaction 66

Figure 3.7 GPC curve of mixed sample 68

Figure 3.8 The figure shows that larger molecules which continued

down the columns and eluted faster whereas smaller

molecules can penetrate the pores of the columns and are

therefore retained to a greater extent than the larger

molecules.

68

Figure 3.9 Finish toner prepared by using resin M30 was observed by

using microscope under magnification 100, the toner

particles were found in irregular shape.

78

Figure 3.10 Finish toner prepared by using resin SJ700 was observed by

using microscope under magnification 100, the toner

particles were found in irregular shape.

79

List of Table

xiv

Table 1.1 Examples of common print defects 7

Table 1.2 Comparison between various processes of polymerization 10,11

Table 1.3 Examples of crosslinking agents for synthesis of styrene

acrylic copolymer

18

Table 2.1 Formulation for preparation of low molecular weight resin

by solution polymerization at 130C

24

Table 2.2 Formulation for preparation of high molecular weight resin 26

Table 2.3 Formulation for preparation of mixing between high and

low molecular weight resins

30

Table 2.4 Formulation for pilot line processing to produce raw toner 37

Table 2.5 Formulation for final blending to produce finished toner 37

Table 3.1 Formulation and properties results for low molecular

weight resin

57

Table 3.2 Formulation and properties results for high molecular

weight resin prepared by using 2 parts MAA by weight

60

Table 3.3 Formulation and properties results for high molecular

weight resin prepared by using 3 parts MAA by weight

61

Table 3.4 Formulation and properties results for mixed sample M28

to M31

71

Table 3.5 Formulation and properties results for mixed sample M40

to M43

72

Table 3.6 Properties results for commercial resins 74

Table 3.7 Comparison between commercial resins, patent literature

and experimental samples

76

Table 3.8 Comparison of properties between finished toner produced

by using M30 and SJ700.

77

xvi

List of abbreviations

MAA Methacrylic acid

TD Tetra ethylene glycol diacrylate

GPC Gel permeation chromatography

DSC Differential scanning calorimetry

MFI Melt flow indexes

TSC Total solid content

AN Acid number

MWD Molecular weight distribution

Tg Glass transition temperature

Mn Number average molecular weight

Mw Weight average molecular weight

Mz Z average molecular weight

Mp Peak value for molecular weight distribution

Ip Polydispersity of molecular weight

Al aluminium

THF Tetrahydrofuran

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Preparation of Styrene Acrylic